WO2012133582A1 - Method for producing fluorine-containing copolymer - Google Patents

Method for producing fluorine-containing copolymer Download PDF

Info

Publication number
WO2012133582A1
WO2012133582A1 PCT/JP2012/058238 JP2012058238W WO2012133582A1 WO 2012133582 A1 WO2012133582 A1 WO 2012133582A1 JP 2012058238 W JP2012058238 W JP 2012058238W WO 2012133582 A1 WO2012133582 A1 WO 2012133582A1
Authority
WO
WIPO (PCT)
Prior art keywords
emulsifier
monomer
vinyl
sodium
hydrocarbon
Prior art date
Application number
PCT/JP2012/058238
Other languages
French (fr)
Japanese (ja)
Inventor
裕司 今堀
裕俊 吉田
真由美 飯田
剣吾 伊藤
田中　義人
井本　克彦
琢磨 川部
Original Assignee
ダイキン工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ダイキン工業株式会社 filed Critical ダイキン工業株式会社
Priority to EP12764488.8A priority Critical patent/EP2692750A4/en
Priority to US14/008,617 priority patent/US20150240012A1/en
Priority to CN2012800161337A priority patent/CN103459441A/en
Priority to KR1020137028672A priority patent/KR20130135990A/en
Publication of WO2012133582A1 publication Critical patent/WO2012133582A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/18—Monomers containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/182—Monomers containing fluorine not covered by the groups C08F214/20 - C08F214/28
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/186—Monomers containing fluorine with non-fluorinated comonomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/186—Monomers containing fluorine with non-fluorinated comonomers
    • C08F214/188—Monomers containing fluorine with non-fluorinated comonomers with non-fluorinated vinyl ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/24—Trifluorochloroethene
    • C08F214/245—Trifluorochloroethene with non-fluorinated comonomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/26—Tetrafluoroethene
    • C08F214/265—Tetrafluoroethene with non-fluorinated comonomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • C08F218/08—Vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/24—Trifluorochloroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/26—Tetrafluoroethene

Definitions

  • the present invention relates to a method for producing a copolymer containing a perhaloolefin and vinyl acetate by a novel emulsion polymerization method.
  • Fluorine-containing copolymers exhibit excellent chemical resistance, solvent resistance, heat resistance, and antifouling properties, and are used as raw materials for various products that take advantage of these properties. It is used in a wide range of industrial fields such as paints.
  • fluorine-containing copolymers are produced by emulsion polymerization, suspension polymerization or solution polymerization of fluoroolefin.
  • a surfactant is used in the emulsion polymerization method.
  • the amount of the surfactant used increases, the number of polymer particles generated at the initial stage of the emulsion polymerization increases, and the polymerization rate increases.
  • the production efficiency of the polymer is improved.
  • a surfactant is used in a large amount, various physical properties such as water resistance of the fluorine-containing copolymer from which the surfactant is obtained tend to be lowered. Therefore, there has been a demand for the development of a production method that can be efficiently polymerized in the presence of a small amount of a surfactant and that does not adversely affect the physical properties of the fluorinated copolymer.
  • Patent Documents 1 to 3 expensive ammonium perfluorooctanoate is used in emulsion polymerization of a copolymer of fluoroolefin and vinyl acetate.
  • Patent Document 4 proposes a method for producing a fluorinated copolymer using a linear aliphatic sulfonate surfactant.
  • Patent Document 5 a production method using alkylphosphonic acid or an ester thereof as a non-fluorine surfactant is used.
  • Patent Document 6 a compound in which phosphoric acid, sulfonic acid, carboxylic acid, or the like is bonded to a quaternary carbon atom. A method of using it has been proposed.
  • An object of this invention is to provide the manufacturing method by the novel emulsion polymerization method of the copolymer containing a perhaloolefin and vinyl acetate.
  • the present invention is a hydrocarbon emulsifier (provided that the formula (1): (Wherein R 1 and R 2 are the same or different, and both are non-fluorinated saturated hydrocarbon groups having 4 to 12 carbon atoms; M is an alkali metal, ammonium salt or amine salt) And a perhaloolefin-vinyl acetate copolymer produced by emulsion polymerization of at least a perhaloolefin having 2 carbon atoms and vinyl acetate in the presence of a non-emulsifier.
  • sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium decyl sulfate, sodium decyl sulfonate, sodium tetradecyl sulfate or sodium tetradecane sulfonate is preferable.
  • a fluorine-containing polymer can be produced without using an expensive fluorine-based emulsifier generally used in emulsion polymerization of a fluorine-containing polymer.
  • the process for producing a perhaloolefin-vinyl acetate copolymer of the present invention is carried out in the presence of a specific hydrocarbon emulsifier or an emulsifier when copolymerizing at least a C 2 perhaloolefin and vinyl acetate by an emulsion polymerization method. It is performed in the absence of.
  • the monomer polymerized by the production method of the present invention is a perhaloolefin having 2 carbon atoms and vinyl acetate, and if necessary, other copolymerizable non-fluorinated monomers.
  • the perhaloolefin having 2 carbon atoms is preferably tetrafluoroethylene (TFE) and chlorotrifluoroethylene (CTFE).
  • the vinyl acetate (mol% ratio) is preferably 20 to 80/80 to 20, and more preferably 35 to 65/65 to 35.
  • Examples of other copolymerizable non-fluorinated monomers include crosslinkable group-free monomers such as non-fluorinated vinyl monomers, and non-fluorinated crosslinkable group-containing monomers.
  • Non-fluorinated vinyl monomers include, for example, olefins such as ethylene, propylene, isobutylene and n-butene; vinyl ethers such as ethyl vinyl ether, cyclohexyl vinyl ether and methyl vinyl ether; vinyl versatate, vinyl benzoate, vinyl pivalate, laurin
  • vinyl esters such as vinyl acid vinyl, vinyl stearate, and vinyl cyclohexylcarboxylate. Among them, from the viewpoint of improving compatibility when used as a paint, coating film hardness, transparency of the coating film, and film forming properties. Ethyl vinyl ether, cyclohexyl vinyl ether, and vinyl versatate are preferred.
  • Non-fluorine crosslinkable group-containing monomers include undecylenic acid, crotonic acid, maleic acid, maleic acid monoester, vinyl acetic acid, cinnamic acid, 3-allyloxypropionic acid, itaconic acid, itaconic acid monoester and the like.
  • (perhaloolefin) / (vinyl acetate and non-fluorinated monomers) ) (Mol% ratio) is preferably 20 to 80/80 to 20, more preferably 35 to 65/65 to 35.
  • the monomer unit based on the non-fluorine-based crosslinkable group-containing monomer is 0.1 to 10 mol% in the copolymer, and further 1 to 10 mol from the viewpoint of improving the solvent resistance and weather resistance of the cured coating film. % Is preferably included.
  • emulsion polymerization is carried out in the presence of a hydrocarbon-based emulsifier or in the absence of an emulsifier.
  • the simple term “emulsifier” includes not only hydrocarbon emulsifiers but also fluorine emulsifiers and other emulsifiers. That is, the “emulsifier” includes all compounds generally called emulsifiers. Therefore, “emulsion polymerization is carried out in the absence of an emulsifier” means that the emulsion polymerization is carried out without using any compound generally classified as an emulsifier.
  • hydrocarbon-based emulsifier a hydrocarbon-based emulsifier excluding the following compound (1) is used.
  • Compound (1) Formula (1) (Wherein R 1 and R 2 are the same or different and both are non-fluorinated saturated hydrocarbon groups having 4 to 12 carbon atoms; M is an alkali metal, ammonium salt or amine salt).
  • the alkali metal salt of dialkylsulfosuccinic acid contained in the formula (1) is known as an emulsifier for emulsion polymerization, and WO 2002/010237 pamphlet describes a monomer containing a fluoroolefin as a nonionic emulsifier and an anion.
  • An alkali metal salt of dialkylsulfosuccinic acid may be added to an aqueous dispersion of a fluororesin obtained by emulsion polymerization using a functional emulsifier in order to improve mechanical stability and thermal stability. It is disclosed.
  • the compound (1) include sodium dioctylsulfosuccinate, sodium didecylsulfosuccinate, sodium dihexylsulfosuccinate, sodium diisobutylsulfosuccinate, sodium diamylsulfosuccinate, ammonium dioctylsulfosuccinate and the like.
  • the emulsifiers used in the present invention include, for example, anionic emulsifiers such as alkylbenzene sulfonates, higher fatty acid salts, alkyl sulfate esters, alkyl sulfonates, and alkyl ether sulfates. can give.
  • CH 3 (CH 2 ) n SO 3 M, CH 3 (CH 2 ) m SO 4 M, CH 3 (CH 2 ) o COOM, H (CH 2 ) p COO (CH 2 CH 2 O ) Q H, (NaSO 3 ) CH ((CH 2 ) r CH 3 ) ((CH 2 ) s CH 3 ) (wherein M is a monovalent cation; n is an integer from 2 to 16; m is from 2 to And hydrocarbon emulsifiers such as o is an integer of 2 to 16, p is an integer of 2 to 40, q is an integer of 2 to 45, and r + s 10 to 20).
  • sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium decyl sulfate, sodium decyl sulfonate, sodium tetradecyl sulfate, sodium tetradecane sulfonate, etc. are inexpensive and have good water solubility and surfactant activity. preferable.
  • the amount of the hydrocarbon-based emulsifier used may be appropriately selected depending on the type of the emulsifier.
  • the amount is preferably 10 to 100,000 ppm, more preferably 500 to 50,000 ppm based on the total amount of water. Of these, 2000 to 40000 ppm, particularly 4000 to 30000 ppm is preferable.
  • the amount of the emulsifier used is less than 10 ppm, the surface activity tends to decrease and the number of generated particles tends to decrease.
  • the emulsion polymerization proceeds sufficiently stably, but a fluorine-based emulsifier and a non-fluorine-based nonionic emulsifier may be used in combination as long as the amount is small.
  • emulsion polymerization proceeds without the presence of an emulsifier.
  • the particle size of the emulsion produced by using the emulsifier is small and the stability is improved.
  • the emulsifiers it is particularly preferable to use the hydrocarbon emulsifier described above from the viewpoint of cost reduction.
  • the polymerization temperature is not particularly limited, and an optimum temperature is adopted according to the kind of the polymerization initiator. However, if it is too high, the monomer density in the gas phase portion may easily decrease, or a branching reaction of the copolymer may occur, and the desired copolymer may not be obtained.
  • the temperature is preferably 40 to 120 ° C, more preferably 50 to 100 ° C.
  • the monomer may be supplied continuously or sequentially.
  • oil-soluble peroxides can also be used. These typical oil-soluble initiators such as diisopropyl peroxydicarbonate (IPP) and di-n-propyl peroxydicarbonate (NPP) These peroxycarbonates have a risk of explosion and the like, are expensive, and have a problem that scales easily adhere to the wall of the polymerization tank during the polymerization reaction. In order to further reduce the compression set of the fluoropolymer, it is preferable to use a water-soluble radical polymerization initiator.
  • IPP isopropyl peroxydicarbonate
  • NPP di-n-propyl peroxydicarbonate
  • water-soluble radical polymerization initiator In order to further reduce the compression set of the fluoropolymer, it is preferable to use a water-soluble radical polymerization initiator.
  • water-soluble radical polymerization initiator examples include persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, ammonium percarbonate, potassium salt, sodium salt, and the like. Particularly, ammonium persulfate and potassium persulfate are used. preferable.
  • the addition amount of the polymerization initiator is not particularly limited, but it is added all at once in the initial stage of polymerization, sequentially or continuously, such that the polymerization rate is not significantly reduced (for example, several ppm to water concentration). do it.
  • the upper limit is a range in which the heat of polymerization reaction can be removed from the surface of the apparatus.
  • a molecular weight regulator or the like may be further added.
  • the molecular weight modifier may be added all at once in the initial stage, or may be added continuously or dividedly.
  • the molecular weight regulator examples include esters such as dimethyl malonate, diethyl malonate, methyl acetate, ethyl acetate, butyl acetate, dimethyl succinate, isopentane, isopropanol, acetone, various mercaptans, carbon tetrachloride, cyclohexane, mono Examples thereof include iodomethane, 1-iodomethane, 1-iodopropane, isopropyl iodide, diiodomethane, 1,2-diiodomethane, 1,3-diiodopropane and the like.
  • a buffering agent or the like may be added as appropriate, but the amount is preferably used within a range not impairing the effects of the present invention.
  • the polymerization pressure may be appropriately selected within the range of 0.1 to 10 MPa, and further 0.2 to 8 MPa. Within this range, the pressure may be low (0.1 to 1 MPa) or high (1 to 10 MPa).
  • the stirring means for example, an anchor blade, a turbine blade, an inclined blade, or the like can be used. However, stirring with a large blade called a full zone or max blend is preferable from the viewpoint of good monomer diffusion and polymer dispersion stability.
  • the stirring device may be a horizontal stirring device or a vertical stirring device.
  • an emulsion of a perhaloolefin-vinyl acetate copolymer having a small particle size and excellent stability in an emulsion can be produced.
  • the perhaloolefin-vinyl acetate copolymer obtained by the production method of the present invention preferably has a particle size (average particle size) of 10 to 400 nm. More preferably, it is 40 to 380 nm.
  • the particle size can be measured using a laser light scattering particle size measuring device (trade name ELS-3000, manufactured by Otsuka Electronics Co., Ltd.).
  • the perhaloolefin-vinyl acetate copolymer obtained by the production method of the present invention preferably has a glass transition temperature of 20 to 80 ° C. More preferably, it is 30 to 70 ° C.
  • the glass transition temperature can be measured by a differential scanning calorimeter (DSC).
  • the measuring method of various physical properties is as follows.
  • Example 1 In a 0.5 L stainless steel autoclave, 250 g of pure water, 0.138 g of sodium dodecyl sulfate (SDS) (with respect to polymerization water of 554 ppm) and 5.8 g of vinyl acetate (VAc) were substituted with nitrogen, and 5 g of tetrafluoroethylene (TFE) was added. In addition, the temperature in the tank was raised to 80 ° C. Thereafter, 4 g of TFE was added. At this time, the pressure in the tank was 0.800 MPa. With stirring, 2.5 g of a 1.0 mass% aqueous solution of ammonium persulfate (APS) was added to start the reaction. The addition of VAc was started at the start of the reaction, and 18.7 g of VAc was added over 4 hours. During the reaction, TFE was continuously supplied using a solenoid valve. The stirring speed was 700 rpm.
  • SDS sodium dodecyl sulfate
  • VAc vinyl acetate
  • the solenoid valve When TFE is consumed and the inside of the tank reaches 0.800 MPa, the solenoid valve is automatically opened and TFE is supplied, and when 0.775 MPa is reached, the solenoid valve is automatically closed and the supply of TFE is stopped. And controlled the pressure.
  • the obtained TFE / VAc copolymer had a glass transition temperature of 30 ° C. and a particle size of 82 nm.
  • Example 2 A 0.5 L stainless steel autoclave was charged with 250 g of pure water and 5.8 g of VAc, purged with nitrogen, 4 g of TFE was added, and the temperature in the tank was raised to 80 ° C. Thereafter, 3 g of TFE was added. At this time, the pressure in the tank was 0.800 MPa. With stirring, 2.5 g of a 0.2 mass% aqueous solution of APS was added to start the reaction. The addition of VAc was started at the start of the reaction, and 7.1 g of VAc was added over 2 hours. During the reaction, TFE was continuously supplied using a solenoid valve. The stirring speed was 700 rpm.
  • the solenoid valve When TFE is consumed and the inside of the tank reaches 0.800 MPa, the solenoid valve is automatically opened and TFE is supplied, and when 0.775 MPa is reached, the solenoid valve is automatically closed and the supply of TFE is stopped. And controlled the pressure.
  • the obtained TFE / VAc copolymer had a glass transition temperature of 35 ° C. and a particle size of 213 nm.
  • Example 3 A 0.5 L stainless steel autoclave was charged with 250 g of pure water and 4.7 g of VAc, and the atmosphere was replaced with nitrogen. 36 g of chlorotrifluoroethylene (CTFE) was added, and the temperature in the tank was raised to 60 ° C. While stirring, 2.5 g of a 2.0 mass% aqueous solution of APS was added to start the reaction. VAc addition was started at the start of the reaction and 6.1 g VAc was added over 1 hour. The stirring speed was 700 rpm.
  • CTFE chlorotrifluoroethylene
  • the obtained CTFE / VAc copolymer had a glass transition temperature of 62 ° C. and a particle size of 370 nm.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

A method for producing a copolymer containing a perhaloolefin and vinyl acetate using a novel emulsion polymerization method is provided. The method for producing the perhaloolefin-vinyl acetate copolymer is characterized in that a perhaloolefin with at least 2 carbons and vinyl acetate are subjected to emulsion polymerization in the presence of an emulsifier, or in the presence of a hydrocarbon emulsifier (excluding compound (1) represented by formula (1)). [Formula 1] (In the formula, R1 and R2 are the same or different, and both represent a non-fluorinated saturated hydrocarbon group; and M represents an alkali metal, an ammonium salt or an amine salt).

Description

含フッ素共重合体の製造方法Method for producing fluorine-containing copolymer
本発明は、パーハロオレフィンと酢酸ビニルとを含む共重合体の新規な乳化重合法による製造方法に関する。 The present invention relates to a method for producing a copolymer containing a perhaloolefin and vinyl acetate by a novel emulsion polymerization method.
含フッ素共重合体は、その卓越した耐薬品性、耐溶剤性、耐熱性、防汚性を示すことから、これらの特性を活かした各種の製品の原料として、自動車工業、半導体工業、化学工業、塗料等の広い産業分野において使用されている。 Fluorine-containing copolymers exhibit excellent chemical resistance, solvent resistance, heat resistance, and antifouling properties, and are used as raw materials for various products that take advantage of these properties. It is used in a wide range of industrial fields such as paints.
これらの含フッ素共重合体の製造は、フルオロオレフィンを乳化重合、懸濁重合または溶液重合することにより行われている。通常、乳化重合法では界面活性剤が使用されるが、界面活性剤の使用量が多くなるほど、乳化重合の初期に生成する重合体粒子の数が増え、その重合速度は早くなり、含フッ素共重合体の生産効率が向上する。しかし、界面活性剤を多量に使用した場合、界面活性剤が得られた含フッ素共重合体の耐水性などの諸物性を低下させる傾向がある。そのため、従来から、少量の界面活性剤の存在下で、効率よく重合ができ、かつ、含フッ素共重合体の諸物性に悪影響を与えることのない製造方法の開発が望まれていた。 These fluorine-containing copolymers are produced by emulsion polymerization, suspension polymerization or solution polymerization of fluoroolefin. Usually, a surfactant is used in the emulsion polymerization method. However, as the amount of the surfactant used increases, the number of polymer particles generated at the initial stage of the emulsion polymerization increases, and the polymerization rate increases. The production efficiency of the polymer is improved. However, when a surfactant is used in a large amount, various physical properties such as water resistance of the fluorine-containing copolymer from which the surfactant is obtained tend to be lowered. Therefore, there has been a demand for the development of a production method that can be efficiently polymerized in the presence of a small amount of a surfactant and that does not adversely affect the physical properties of the fluorinated copolymer.
このような状況下、フルオロオレフィンと酢酸ビニルとの共重合体の乳化重合では高価なパーフルオロオクタン酸アンモニウムが使用されている（特許文献１～３）。 Under such circumstances, expensive ammonium perfluorooctanoate is used in emulsion polymerization of a copolymer of fluoroolefin and vinyl acetate (Patent Documents 1 to 3).
フルオロオレフィンを含む共重合体の乳化重合にフッ素系の乳化剤以外の乳化剤を使用した例もある。たとえば特許文献４では、直鎖の脂肪族スルホン酸塩系の界面活性剤を使用した含フッ素共重合体の製造方法が提案されている。また、特許文献５では非フッ素系の界面活性剤として、アルキルホスホン酸またはそのエステルを用いる製造方法が、特許文献６では４級炭素原子にリン酸やスルホン酸、カルボン酸などが結合した化合物を用いる方法が提案されている。フルオロオレフィンと酢酸ビニルとの共重合に使用された例は知らない。 There is also an example in which an emulsifier other than a fluorine-based emulsifier is used for emulsion polymerization of a copolymer containing a fluoroolefin. For example, Patent Document 4 proposes a method for producing a fluorinated copolymer using a linear aliphatic sulfonate surfactant. In Patent Document 5, a production method using alkylphosphonic acid or an ester thereof as a non-fluorine surfactant is used. In Patent Document 6, a compound in which phosphoric acid, sulfonic acid, carboxylic acid, or the like is bonded to a quaternary carbon atom. A method of using it has been proposed. There is no known example used for copolymerization of fluoroolefin and vinyl acetate.
米国特許第５０７０１６２号明細書US Pat. No. 5,070,162 米国特許第５０３２６５６号明細書US Pat. No. 5,032,656 特許第３９３７４４９号明細書Japanese Patent No. 3937449 米国特許第６５１２０６３号明細書US Pat. No. 6512063 米国特許出願公開第２００７／００３２５９１号明細書US Patent Application Publication No. 2007/0032591 国際公開第２００５／０６３８２７号International Publication No. 2005/063827
本発明は、パーハロオレフィンと酢酸ビニルとを含む共重合体の新規な乳化重合法による製造方法を提供することを目的とする。 An object of this invention is to provide the manufacturing method by the novel emulsion polymerization method of the copolymer containing a perhaloolefin and vinyl acetate.
すなわち本発明は、炭化水素系乳化剤（ただし、式（１）：
Figure JPOXMLDOC01-appb-C000002
 （式中、Ｒ１およびＲ２は同じかまたは異なり、いずれも炭素数４～１２の非フッ素系飽和炭化水素基；Ｍはアルカリ金属、アンモニウム塩またはアミン塩）で示される化合物（１）は除く）の存在下または乳化剤の不存在下に、少なくとも、炭素数２のパーハロオレフィンと酢酸ビニルを乳化重合することを特徴とするパーハロオレフィン－酢酸ビニル系共重合体の製造方法に関する。 That is, the present invention is a hydrocarbon emulsifier (provided that the formula (1):
Figure JPOXMLDOC01-appb-C000002
 (Wherein R 1 and R 2 are the same or different, and both are non-fluorinated saturated hydrocarbon groups having 4 to 12 carbon atoms; M is an alkali metal, ammonium salt or amine salt) And a perhaloolefin-vinyl acetate copolymer produced by emulsion polymerization of at least a perhaloolefin having 2 carbon atoms and vinyl acetate in the presence of a non-emulsifier.
炭化水素系乳化剤としては、ドデシル硫酸ナトリウム、ドデシルスルホン酸ナトリウム、デシル硫酸ナトリウム、デシルスルホン酸ナトリウム、テトラデシル硫酸ナトリウムまたはテトラデカンスルホン酸ナトリウムが好ましい。 As the hydrocarbon emulsifier, sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium decyl sulfate, sodium decyl sulfonate, sodium tetradecyl sulfate or sodium tetradecane sulfonate is preferable.
本発明によれば、含フッ素重合体の乳化重合で一般的に使用されている、高価なフッ素系乳化剤を使用せずに含フッ素重合体を製造することができる。 According to the present invention, a fluorine-containing polymer can be produced without using an expensive fluorine-based emulsifier generally used in emulsion polymerization of a fluorine-containing polymer.
本発明のパーハロオレフィン－酢酸ビニル系共重合体の製造方法は、少なくとも炭素数２のパーハロオレフィンと酢酸ビニルを乳化重合法により共重合するに際し、特定の炭化水素系乳化剤の存在下または乳化剤の不存在下に行うことを特徴とする。 The process for producing a perhaloolefin-vinyl acetate copolymer of the present invention is carried out in the presence of a specific hydrocarbon emulsifier or an emulsifier when copolymerizing at least a C 2 perhaloolefin and vinyl acetate by an emulsion polymerization method. It is performed in the absence of.
本発明の製造方法で重合する単量体は、炭素数２のパーハロオレフィンと酢酸ビニルと、要すれば、他の共重合可能な非フッ素系単量体である。 The monomer polymerized by the production method of the present invention is a perhaloolefin having 2 carbon atoms and vinyl acetate, and if necessary, other copolymerizable non-fluorinated monomers.
炭素数２のパーハロオレフィンはテトラフルオロエチレン（ＴＦＥ）およびクロロトリフルオロエチレン（ＣＴＦＥ）であることが好ましい。 The perhaloolefin having 2 carbon atoms is preferably tetrafluoroethylene (TFE) and chlorotrifluoroethylene (CTFE).
パーハロオレフィンと酢酸ビニルとの２元共重合体の場合、すなわち、上記パーハロオレフィン－酢酸ビニル系共重合体がパーハロオレフィンの１種及び酢酸ビニルのみから形成される場合、パーハロオレフィン／酢酸ビニル（ｍｏｌ％比）で２０～８０／８０～２０であることが好ましく、さらには３５～６５／６５～３５であることが好ましい。 In the case of a binary copolymer of perhaloolefin and vinyl acetate, that is, when the perhaloolefin-vinyl acetate copolymer is formed from only one perhaloolefin and vinyl acetate, The vinyl acetate (mol% ratio) is preferably 20 to 80/80 to 20, and more preferably 35 to 65/65 to 35.
他の共重合可能な非フッ素系単量体としては、たとえば非フッ素系ビニル単量体などの架橋性基不含有単量体、または非フッ素系架橋性基含有単量体などがあげられる。 Examples of other copolymerizable non-fluorinated monomers include crosslinkable group-free monomers such as non-fluorinated vinyl monomers, and non-fluorinated crosslinkable group-containing monomers.
非フッ素系ビニル単量体としては、たとえばエチレン、プロピレン、イソブチレン、ｎ－ブテンなどのオレフィン；エチルビニルエーテル、シクロヘキシルビニルエーテル、メチルビニルエーテルなどのビニルエーテル；バーサティック酸ビニル、安息香酸ビニル、ピバリン酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、シクロヘキシルカルボン酸ビニルなどのビニルエステルなどがあげられ、なかでも、塗料として用いた際の相溶性、塗膜硬度、塗膜の透明性、造膜性を向上させる点からエチルビニルエーテル、シクロヘキシルビニルエーテル、バーサティック酸ビニルが好ましい。 Non-fluorinated vinyl monomers include, for example, olefins such as ethylene, propylene, isobutylene and n-butene; vinyl ethers such as ethyl vinyl ether, cyclohexyl vinyl ether and methyl vinyl ether; vinyl versatate, vinyl benzoate, vinyl pivalate, laurin Examples include vinyl esters such as vinyl acid vinyl, vinyl stearate, and vinyl cyclohexylcarboxylate. Among them, from the viewpoint of improving compatibility when used as a paint, coating film hardness, transparency of the coating film, and film forming properties. Ethyl vinyl ether, cyclohexyl vinyl ether, and vinyl versatate are preferred.
非フッ素系架橋性基含有単量体としては、ウンデシレン酸、クロトン酸、マレイン酸、マレイン酸モノエステル、ビニル酢酸、桂皮酸、３－アリルオキシプロピオン酸、イタコン酸、イタコン酸モノエステルなどの不飽和カルボン酸；２－ヒドロキシエチルビニルエーテル、３－ヒドロキシプロピルビニルエーテル、２－ヒドロキシプロピルビニルエーテル、２－ヒドロキシ－２－メチルプロピルビニルエーテル、４－ヒドロキシブチルビニルエーテル、４－ヒドロキシ－２－メチルブチルビニルエーテル、５－ヒドロキシペンチルビニルエーテル、６－ヒドロキシヘキシルビニルエーテル、２－ヒドロキシエチルアリルエーテル、４－ヒドロキシブチルアリルエーテル、グリセロールモノアリルエーテルなどの水酸基含有ビニル単量体などが例示できる。なかでも重合反応性、硬化性が優れる点から２－ヒドロキシエチルビニルエーテル、４－ヒドロキシブチルビニルエーテル、ウンデシレン酸、クロトン酸が好ましい。 Non-fluorine crosslinkable group-containing monomers include undecylenic acid, crotonic acid, maleic acid, maleic acid monoester, vinyl acetic acid, cinnamic acid, 3-allyloxypropionic acid, itaconic acid, itaconic acid monoester and the like. Saturated carboxylic acid; 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether, 5- Hydroxyl-containing vinyl monomers such as hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether, etc. It can be exemplified. Of these, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, undecylenic acid, and crotonic acid are preferable from the viewpoint of excellent polymerization reactivity and curability.
また、パーハロオレフィン及び酢酸ビニルにこれらの非フッ素系単量体を共重合して３元以上の共重合体とする場合は、（パーハロオレフィン）／（酢酸ビニルと非フッ素系単量体の合計）（ｍｏｌ％比）が２０～８０／８０～２０であることが好ましく、さらには３５～６５／６５～３５であることが好ましい。 When these non-fluorinated monomers are copolymerized with perhaloolefin and vinyl acetate to form a ternary or higher copolymer, (perhaloolefin) / (vinyl acetate and non-fluorinated monomers) ) (Mol% ratio) is preferably 20 to 80/80 to 20, more preferably 35 to 65/65 to 35.
非フッ素系架橋性基含有単量体に基づく単量体単位は、共重合体中に０．１～１０ｍｏｌ％、さらには硬化塗膜の耐溶剤性、耐候性の向上の点から１～１０ｍｏｌ％含まれることが好ましい。 The monomer unit based on the non-fluorine-based crosslinkable group-containing monomer is 0.1 to 10 mol% in the copolymer, and further 1 to 10 mol from the viewpoint of improving the solvent resistance and weather resistance of the cured coating film. % Is preferably included.
本発明では、乳化重合を炭化水素系乳化剤の存在下、または乳化剤の不存在下で行う。
本明細書において、単に「乳化剤」という場合、炭化水素系乳化剤だけでなく、フッ素系乳化剤やその他の乳化剤をも含むものとする。すなわち、「乳化剤」には、一般に乳化剤と称されるあらゆる化合物が含まれる。従って、「乳化重合を乳化剤の不存在下で行う」とは、乳化重合を、一般に乳化剤に分類される化合物を一切使用せずに行うことを意味する。 In the present invention, emulsion polymerization is carried out in the presence of a hydrocarbon-based emulsifier or in the absence of an emulsifier.
In the present specification, the simple term “emulsifier” includes not only hydrocarbon emulsifiers but also fluorine emulsifiers and other emulsifiers. That is, the “emulsifier” includes all compounds generally called emulsifiers. Therefore, “emulsion polymerization is carried out in the absence of an emulsifier” means that the emulsion polymerization is carried out without using any compound generally classified as an emulsifier.
炭化水素系乳化剤としては、つぎの化合物（１）を除く炭化水素系乳化剤を用いる。 As the hydrocarbon-based emulsifier, a hydrocarbon-based emulsifier excluding the following compound (1) is used.
化合物（１）
式（１）：
Figure JPOXMLDOC01-appb-C000003
 （式中、Ｒ１およびＲ２は同じかまたは異なり、いずれも炭素数４～１２の非フッ素系飽和炭化水素基；Ｍはアルカリ金属、アンモニウム塩またはアミン塩）で示される化合物である。 Compound (1)
Formula (1):
Figure JPOXMLDOC01-appb-C000003
 (Wherein R 1 and R 2 are the same or different and both are non-fluorinated saturated hydrocarbon groups having 4 to 12 carbon atoms; M is an alkali metal, ammonium salt or amine salt).
式（１）に含まれるジアルキルスルホコハク酸のアルカリ金属塩は乳化重合用の乳化剤として知られており、国際公開第２００２／０１０２３７号パンフレットには、フルオロオレフィンを含む単量体をノニオン性乳化剤とアニオン性乳化剤を併用して乳化重合して得られたフッ素樹脂の水性分散液に、機械的安定性や熱的安定性の改善のためにジアルキルスルホコハク酸のアルカリ金属塩を添加してもよいことが開示されている。 The alkali metal salt of dialkylsulfosuccinic acid contained in the formula (1) is known as an emulsifier for emulsion polymerization, and WO 2002/010237 pamphlet describes a monomer containing a fluoroolefin as a nonionic emulsifier and an anion. An alkali metal salt of dialkylsulfosuccinic acid may be added to an aqueous dispersion of a fluororesin obtained by emulsion polymerization using a functional emulsifier in order to improve mechanical stability and thermal stability. It is disclosed.
化合物（１）の具体例としては、たとえばジオクチルスルホコハク酸ナトリウム、ジデシルスルホコハク酸ナトリウム、ジヘキシルスルホコハク酸ナトリウム、ジイソブチルスルホコハク酸ナトリウム、ジアミルスルホコハク酸ナトリウム、ジオクチルスルホコハク酸アンモニウムなどがあげられる。 Specific examples of the compound (1) include sodium dioctylsulfosuccinate, sodium didecylsulfosuccinate, sodium dihexylsulfosuccinate, sodium diisobutylsulfosuccinate, sodium diamylsulfosuccinate, ammonium dioctylsulfosuccinate and the like.
化合物（１）以外の炭化水素系乳化剤として、本発明で用いる乳化剤は、たとえばアルキルベンゼンスルホン酸塩、高級脂肪酸塩、アルキル硫酸エステル塩、アルキルスルホン酸塩、アルキルエーテル硫酸塩等のアニオン性乳化剤などがあげられる。 As hydrocarbon-based emulsifiers other than compound (1), the emulsifiers used in the present invention include, for example, anionic emulsifiers such as alkylbenzene sulfonates, higher fatty acid salts, alkyl sulfate esters, alkyl sulfonates, and alkyl ether sulfates. can give.
具体的には、たとえばＣＨ３（ＣＨ２）ｎＳＯ３Ｍ、ＣＨ３（ＣＨ２）ｍＳＯ４Ｍ、ＣＨ３（ＣＨ２）ｏＣＯＯＭ、Ｈ（ＣＨ２）ｐＣＯＯ（ＣＨ２ＣＨ２Ｏ）ｑＨ、（ＮａＳＯ３）ＣＨ（（ＣＨ２）ｒＣＨ３）（（ＣＨ２）ｓＣＨ３）（式中、Ｍは１価のカチオン；ｎは２～１６の整数；ｍは２～１６の整数；ｏは２～１６の整数；ｐは２～４０の整数；ｑは２～４５の整数；ｒ＋ｓ＝１０～２０）などの炭化水素系乳化剤があげられる。なかでも、安価であることや乳化剤の水溶性や界面活性作用が良好であることからドデシル硫酸ナトリウム、ドデシルスルホン酸ナトリウム、デシル硫酸ナトリウム、デシルスルホン酸ナトリウム、テトラデシル硫酸ナトリウム、テトラデカンスルホン酸ナトリウムなどが好ましい。 Specifically, for example, CH 3 (CH 2 ) n SO 3 M, CH 3 (CH 2 ) m SO 4 M, CH 3 (CH 2 ) o COOM, H (CH 2 ) p COO (CH 2 CH 2 O ) Q H, (NaSO 3 ) CH ((CH 2 ) r CH 3 ) ((CH 2 ) s CH 3 ) (wherein M is a monovalent cation; n is an integer from 2 to 16; m is from 2 to And hydrocarbon emulsifiers such as o is an integer of 2 to 16, p is an integer of 2 to 40, q is an integer of 2 to 45, and r + s = 10 to 20). Among them, sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium decyl sulfate, sodium decyl sulfonate, sodium tetradecyl sulfate, sodium tetradecane sulfonate, etc., are inexpensive and have good water solubility and surfactant activity. preferable.
炭化水素系乳化剤の使用量は乳化剤の種類によって適宜選定すればよいが、たとえば水の全量に対し、１０～１０００００ｐｐｍが好ましく、５００～５００００ｐｐｍがより好ましい。なかでも、２０００～４００００ｐｐｍ、特に４０００～３００００ｐｐｍが好ましい。前記乳化剤の使用量が、１０ｐｐｍ未満であると、界面活性能が小さくなり発生粒子数が少なくなる傾向にある。 The amount of the hydrocarbon-based emulsifier used may be appropriately selected depending on the type of the emulsifier. For example, the amount is preferably 10 to 100,000 ppm, more preferably 500 to 50,000 ppm based on the total amount of water. Of these, 2000 to 40000 ppm, particularly 4000 to 30000 ppm is preferable. When the amount of the emulsifier used is less than 10 ppm, the surface activity tends to decrease and the number of generated particles tends to decrease.
また、炭化水素系乳化剤は単独で使用しても十分に乳化重合が安定して進むが、少量であればフッ素系の乳化剤、非フッ素系ノニオン性乳化剤を併用してもよい。 In addition, even when the hydrocarbon-based emulsifier is used alone, the emulsion polymerization proceeds sufficiently stably, but a fluorine-based emulsifier and a non-fluorine-based nonionic emulsifier may be used in combination as long as the amount is small.
本発明の製造方法では、乳化剤を存在させなくても乳化重合が進む。ただし、乳化剤を使用した方が生成したエマルションの粒径が小さく、安定性が良好になる。乳化剤のなかでも、コスト削減の観点からは、上述した炭化水素系乳化剤を使用することが特に好ましい。 In the production method of the present invention, emulsion polymerization proceeds without the presence of an emulsifier. However, the particle size of the emulsion produced by using the emulsifier is small and the stability is improved. Among the emulsifiers, it is particularly preferable to use the hydrocarbon emulsifier described above from the viewpoint of cost reduction.
重合温度は特に制限はなく、重合開始剤の種類にしたがって最適な温度が採用される。ただ、高くなりすぎると気相部分でのモノマー密度が容易に低下したり、共重合体の分岐反応が生じたりし、目的とする共重合体が得られないことがある。好ましくは４０～１２０℃、さらに好ましくは５０～１００℃とする。 The polymerization temperature is not particularly limited, and an optimum temperature is adopted according to the kind of the polymerization initiator. However, if it is too high, the monomer density in the gas phase portion may easily decrease, or a branching reaction of the copolymer may occur, and the desired copolymer may not be obtained. The temperature is preferably 40 to 120 ° C, more preferably 50 to 100 ° C.
単量体は、連続的に供給しても逐次的に供給してもよい。 The monomer may be supplied continuously or sequentially.
重合開始剤としては、油溶性の過酸化物も使用できるが、これらの代表的な油溶性開始剤であるジイソプロピルパーオキシジカーボネート（ＩＰＰ）やジ－ｎ－プロピルパーオキシジカーボネート（ＮＰＰ）などのパーオキシカーボネート類は爆発などの危険性があるうえ、高価であり、しかも重合反応中に重合槽の壁面などにスケールの付着を生じやすいという問題がある。フルオロポリマーの圧縮永久歪みをよりいっそう低下させるためには、水溶性ラジカル重合開始剤を使用することが好ましい。水溶性ラジカル重合開始剤としては、たとえば過硫酸、過ホウ酸、過塩素酸、過リン酸、過炭酸のアンモニウム塩、カリウム塩、ナトリウム塩などが好ましくあげられ、特に過硫酸アンモニウム、過硫酸カリウムが好ましい。 As the polymerization initiator, oil-soluble peroxides can also be used. These typical oil-soluble initiators such as diisopropyl peroxydicarbonate (IPP) and di-n-propyl peroxydicarbonate (NPP) These peroxycarbonates have a risk of explosion and the like, are expensive, and have a problem that scales easily adhere to the wall of the polymerization tank during the polymerization reaction. In order to further reduce the compression set of the fluoropolymer, it is preferable to use a water-soluble radical polymerization initiator. Preferred examples of the water-soluble radical polymerization initiator include persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, ammonium percarbonate, potassium salt, sodium salt, and the like. Particularly, ammonium persulfate and potassium persulfate are used. preferable.
重合開始剤の添加量は特に限定されないが、重合速度が著しく低下しない程度の量（たとえば数ｐｐｍ対水濃度）以上を、重合の初期に一括して、または逐次的に、または連続して添加すればよい。上限は装置面から重合反応熱を除熱できる範囲である。 The addition amount of the polymerization initiator is not particularly limited, but it is added all at once in the initial stage of polymerization, sequentially or continuously, such that the polymerization rate is not significantly reduced (for example, several ppm to water concentration). do it. The upper limit is a range in which the heat of polymerization reaction can be removed from the surface of the apparatus.
本発明の製造方法において、さらに分子量調整剤などを添加してもよい。分子量調整剤は、初期に一括して添加してもよいし、連続的または分割して添加してもよい。 In the production method of the present invention, a molecular weight regulator or the like may be further added. The molecular weight modifier may be added all at once in the initial stage, or may be added continuously or dividedly.
分子量調整剤としては、たとえばマロン酸ジメチル、マロン酸ジエチル、酢酸メチル、酢酸エチル、酢酸ブチル、コハク酸ジメチルなどのエステル類のほか、イソペンタン、イソプロパノール、アセトン、各種メルカプタン、四塩化炭素、シクロヘキサン、モノヨードメタン、１－ヨードメタン、１－ヨードプロパン、ヨウ化イソプロピル、ジヨードメタン、１，２－ジヨードメタン、１，３－ジヨードプロパンなどがあげられる。 Examples of the molecular weight regulator include esters such as dimethyl malonate, diethyl malonate, methyl acetate, ethyl acetate, butyl acetate, dimethyl succinate, isopentane, isopropanol, acetone, various mercaptans, carbon tetrachloride, cyclohexane, mono Examples thereof include iodomethane, 1-iodomethane, 1-iodopropane, isopropyl iodide, diiodomethane, 1,2-diiodomethane, 1,3-diiodopropane and the like.
そのほか緩衝剤などを適宜添加してもよいが、その量は本発明の効果を損なわない範囲で用いることが好ましい。 In addition, a buffering agent or the like may be added as appropriate, but the amount is preferably used within a range not impairing the effects of the present invention.
重合圧力は０．１～１０ＭＰａ、さらには０．２～８ＭＰａの範囲で適宜選択すればよく、この範囲内であれば、低圧（０．１～１ＭＰａ）でも高圧（１～１０ＭＰａ）でもよい。 The polymerization pressure may be appropriately selected within the range of 0.1 to 10 MPa, and further 0.2 to 8 MPa. Within this range, the pressure may be low (0.1 to 1 MPa) or high (1 to 10 MPa).
攪拌手段としては、たとえばアンカー翼、タービン翼、傾斜翼なども使用できるが、モノマーの拡散とポリマーの分散安定性が良好な点からフルゾーンやマックスブレンドと呼ばれる大型翼による攪拌が好ましい。攪拌装置としては横型攪拌装置でも縦型攪拌装置でもよい。 As the stirring means, for example, an anchor blade, a turbine blade, an inclined blade, or the like can be used. However, stirring with a large blade called a full zone or max blend is preferable from the viewpoint of good monomer diffusion and polymer dispersion stability. The stirring device may be a horizontal stirring device or a vertical stirring device.
本発明の製造方法によれば、粒子径が小さくエマルション中での安定性に優れたパーハロオレフィン－酢酸ビニル系共重合体のエマルションを製造することができる。本発明の製造方法によって得られるパーハロオレフィン－酢酸ビニル系共重合体は、粒子径（平均粒子径）が１０～４００ｎｍであることが好ましい。より好ましくは４０～３８０ｎｍである。
上記粒子径は、レーザー光散乱粒径測定装置（大塚電子（株）製、商品名ＥＬＳ－３０００）を用いて測定することができる。 According to the production method of the present invention, an emulsion of a perhaloolefin-vinyl acetate copolymer having a small particle size and excellent stability in an emulsion can be produced. The perhaloolefin-vinyl acetate copolymer obtained by the production method of the present invention preferably has a particle size (average particle size) of 10 to 400 nm. More preferably, it is 40 to 380 nm.
The particle size can be measured using a laser light scattering particle size measuring device (trade name ELS-3000, manufactured by Otsuka Electronics Co., Ltd.).
本発明の製造方法によって得られるパーハロオレフィン－酢酸ビニル系共重合体はまた、ガラス転移温度が２０～８０℃であることが好ましい。より好ましくは３０～７０℃である。
上記ガラス転移温度は、示差走査熱量計（ＤＳＣ）により測定することができる。 The perhaloolefin-vinyl acetate copolymer obtained by the production method of the present invention preferably has a glass transition temperature of 20 to 80 ° C. More preferably, it is 30 to 70 ° C.
The glass transition temperature can be measured by a differential scanning calorimeter (DSC).
つぎに実施例をあげて本発明を具体的に説明するが、本発明はかかる実施例のみに限定されるものではない。 Next, the present invention will be specifically described with reference to examples. However, the present invention is not limited to such examples.
各種物性の測定方法は次のとおりである。 The measuring method of various physical properties is as follows.
（共重合体の粒子径）
レーザー光散乱粒径測定装置（大塚電子（株）製、商品名ＥＬＳ－３０００）を用いて測定する。 (Particle diameter of copolymer)
Measurement is performed using a laser light scattering particle size measuring apparatus (trade name ELS-3000, manufactured by Otsuka Electronics Co., Ltd.).
（共重合体のガラス転移温度）
示差走査熱量計（ＤＳＣ）により測定する。 (Glass transition temperature of copolymer)
Measured with a differential scanning calorimeter (DSC).
実施例１
０．５Ｌステンレス製オートクレーブに純水２５０ｇ、ドデシル硫酸ナトリウム（ＳＤＳ）０．１３８ｇ（対重合水５５４ｐｐｍ）、酢酸ビニル（ＶＡｃ）５．８ｇを入れ、窒素置換し、テトラフルオロエチレン（ＴＦＥ）５ｇを加え、槽内を８０℃まで昇温した。その後、ＴＦＥを４ｇ加えた。このとき槽内の圧力は０．８００ＭＰａとなった。これに撹拌下、過硫酸アンモニウム（ＡＰＳ）の１．０質量％水溶液２．５ｇを加え、反応を開始した。反応開始時にＶＡｃの追加を開始し、４時間かけて１８．７ｇのＶＡｃを追加した。反応中は電磁弁を用いてＴＦＥを連続供給した。撹拌速度は７００ｒｐｍであった。 Example 1
In a 0.5 L stainless steel autoclave, 250 g of pure water, 0.138 g of sodium dodecyl sulfate (SDS) (with respect to polymerization water of 554 ppm) and 5.8 g of vinyl acetate (VAc) were substituted with nitrogen, and 5 g of tetrafluoroethylene (TFE) was added. In addition, the temperature in the tank was raised to 80 ° C. Thereafter, 4 g of TFE was added. At this time, the pressure in the tank was 0.800 MPa. With stirring, 2.5 g of a 1.0 mass% aqueous solution of ammonium persulfate (APS) was added to start the reaction. The addition of VAc was started at the start of the reaction, and 18.7 g of VAc was added over 4 hours. During the reaction, TFE was continuously supplied using a solenoid valve. The stirring speed was 700 rpm.
ＴＦＥが消費されて槽内が０．８００ＭＰａになると自動的に電磁弁を開いてＴＦＥを供給し、０．７７５ＭＰａになると自動的に電磁弁を閉じてＴＦＥの供給を停止するサイクルでＴＦＥの供給と圧力を制御した。 When TFE is consumed and the inside of the tank reaches 0.800 MPa, the solenoid valve is automatically opened and TFE is supplied, and when 0.775 MPa is reached, the solenoid valve is automatically closed and the supply of TFE is stopped. And controlled the pressure.
反応開始から４時間後に、酢酸ビニルの供給を停止した。その後槽内を常温常圧に戻して重合を停止し、ＴＦＥ／ＶＡｃ共重合体のエマルション３０６ｇ（固形分濃度１６質量％）を得た。また、重合後のエマルションには沈降は生じていなかった。 Four hours after the start of the reaction, the supply of vinyl acetate was stopped. Thereafter, the inside of the tank was returned to room temperature and normal pressure to stop the polymerization, and 306 g of a TFE / VAc copolymer emulsion (solid content concentration: 16% by mass) was obtained. In addition, no precipitation occurred in the emulsion after polymerization.
得られたＴＦＥ／ＶＡｃ共重合体のガラス転移温度は３０℃であり、粒子径は８２ｎｍであった。 The obtained TFE / VAc copolymer had a glass transition temperature of 30 ° C. and a particle size of 82 nm.
実施例２
０．５Ｌステンレス製オートクレーブに純水２５０ｇ、ＶＡｃ５．８ｇを入れ、窒素置換し、ＴＦＥ４ｇを加え、槽内を８０℃まで昇温した。その後、ＴＦＥを３ｇ加えた。このとき槽内の圧力は０．８００ＭＰａとなった。これに撹拌下、ＡＰＳの０．２質量％水溶液２．５ｇを加え、反応を開始した。反応開始時にＶＡｃの追加を開始し、２時間かけて７．１ｇのＶＡｃを追加した。反応中は電磁弁を用いてＴＦＥを連続供給した。撹拌速度は７００ｒｐｍであった。 Example 2
A 0.5 L stainless steel autoclave was charged with 250 g of pure water and 5.8 g of VAc, purged with nitrogen, 4 g of TFE was added, and the temperature in the tank was raised to 80 ° C. Thereafter, 3 g of TFE was added. At this time, the pressure in the tank was 0.800 MPa. With stirring, 2.5 g of a 0.2 mass% aqueous solution of APS was added to start the reaction. The addition of VAc was started at the start of the reaction, and 7.1 g of VAc was added over 2 hours. During the reaction, TFE was continuously supplied using a solenoid valve. The stirring speed was 700 rpm.
ＴＦＥが消費されて槽内が０．８００ＭＰａになると自動的に電磁弁を開いてＴＦＥを供給し、０．７７５ＭＰａになると自動的に電磁弁を閉じてＴＦＥの供給を停止するサイクルでＴＦＥの供給と圧力を制御した。 When TFE is consumed and the inside of the tank reaches 0.800 MPa, the solenoid valve is automatically opened and TFE is supplied, and when 0.775 MPa is reached, the solenoid valve is automatically closed and the supply of TFE is stopped. And controlled the pressure.
反応開始から２時間後にＴＦＥとＶＡｃの供給を停止した。その後槽内を常温常圧に戻して重合を停止し、ＴＦＥ／ＶＡｃ共重合体のエマルション２７２ｇ（固形分濃度６．２質量％）を得た。また、重合後のエマルションには沈降は生じていなかった。 Two hours after the start of the reaction, the supply of TFE and VAc was stopped. Thereafter, the inside of the tank was returned to room temperature and normal pressure to stop the polymerization, and 272 g of a TFE / VAc copolymer emulsion (solid content concentration 6.2 mass%) was obtained. In addition, no precipitation occurred in the emulsion after polymerization.
得られたＴＦＥ／ＶＡｃ共重合体のガラス転移温度は３５℃であり、粒子径は２１３ｎｍであった。 The obtained TFE / VAc copolymer had a glass transition temperature of 35 ° C. and a particle size of 213 nm.
実施例３
０．５Ｌステンレス製オートクレーブに純水２５０ｇ、ＶＡｃ４．７ｇを入れ、窒素置換し、クロロトリフルオロエチレン（ＣＴＦＥ）３６ｇを加え、槽内を６０℃まで昇温した。これに撹拌下、ＡＰＳの２．０質量％水溶液２．５ｇを加え、反応を開始した。反応開始時にＶＡｃの追加を開始し、１時間かけて６．１ｇのＶＡｃを追加した。撹拌速度は７００ｒｐｍであった。 Example 3
A 0.5 L stainless steel autoclave was charged with 250 g of pure water and 4.7 g of VAc, and the atmosphere was replaced with nitrogen. 36 g of chlorotrifluoroethylene (CTFE) was added, and the temperature in the tank was raised to 60 ° C. While stirring, 2.5 g of a 2.0 mass% aqueous solution of APS was added to start the reaction. VAc addition was started at the start of the reaction and 6.1 g VAc was added over 1 hour. The stirring speed was 700 rpm.
反応開始から１時間後に、ＶＡｃの供給を停止した。その後槽内を常温常圧に戻して重合を停止し、ＣＴＦＥ／ＶＡｃ共重合体のエマルション２７６ｇ（固形分濃度４．３質量％）を得た。また、重合後のエマルションには沈降は生じていなかった。 One hour after the start of the reaction, the supply of VAc was stopped. Thereafter, the inside of the tank was returned to room temperature and normal pressure to stop the polymerization, and 276 g of a CTFE / VAc copolymer emulsion (solid content concentration 4.3 mass%) was obtained. In addition, no precipitation occurred in the emulsion after polymerization.
得られたＣＴＦＥ／ＶＡｃ共重合体のガラス転移温度は６２℃であり、粒子径は３７０ｎｍであった。 The obtained CTFE / VAc copolymer had a glass transition temperature of 62 ° C. and a particle size of 370 nm.

Claims (9)

  1. 炭化水素系乳化剤（ただし、式（１）：
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ１およびＲ２は同じかまたは異なり、いずれも炭素数４～１２の非フッ素系飽和炭化水素基；Ｍはアルカリ金属、アンモニウム塩またはアミン塩）で示される化合物（１）は除く）の存在下または乳化剤の不存在下に、少なくとも、炭素数２のパーハロオレフィンと酢酸ビニルを乳化重合することを特徴とするパーハロオレフィン－酢酸ビニル系共重合体の製造方法。     Hydrocarbon emulsifier (however, formula (1):
    Figure JPOXMLDOC01-appb-C000001
     (Wherein R 1 and R 2 are the same or different, and both are non-fluorinated saturated hydrocarbon groups having 4 to 12 carbon atoms; M is an alkali metal, ammonium salt or amine salt) In the presence or absence of an emulsifier, and at least emulsion polymerization of a perhaloolefin having 2 carbon atoms and vinyl acetate.
  2. 前記乳化重合を前記炭化水素系乳化剤の存在下で行う請求項１記載の製造方法。 The manufacturing method of Claim 1 which performs the said emulsion polymerization in presence of the said hydrocarbon emulsifier.
  3. 前記炭化水素系乳化剤がアニオン性乳化剤である請求項２記載の製造方法。 The method according to claim 2, wherein the hydrocarbon emulsifier is an anionic emulsifier.
  4. 前記炭化水素系乳化剤がアルキルベンゼンスルホン酸塩、高級脂肪酸塩、アルキル硫酸エステル塩、アルキルスルホン酸塩、またはアルキルエーテル硫酸塩である請求項２又は３記載の製造方法。 The production method according to claim 2 or 3, wherein the hydrocarbon emulsifier is an alkylbenzene sulfonate, a higher fatty acid salt, an alkyl sulfate salt, an alkyl sulfonate, or an alkyl ether sulfate.
  5. 前記炭化水素系乳化剤が、ドデシル硫酸ナトリウム、ドデシルスルホン酸ナトリウム、デシル硫酸ナトリウム、デシルスルホン酸ナトリウム、テトラデシル硫酸ナトリウムまたはテトラデカンスルホン酸ナトリウムである請求項２～４のいずれか１項記載の製造方法。 The production method according to any one of claims 2 to 4, wherein the hydrocarbon emulsifier is sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium decyl sulfate, sodium decyl sulfonate, sodium tetradecyl sulfate or sodium tetradecane sulfonate.
  6. 炭素数２のパーハロオレフィンと酢酸ビニルに加えて非フッ素系単量体を共重合する請求項１～５のいずれか１項に記載の製造方法。 The production method according to any one of claims 1 to 5, wherein a non-fluorinated monomer is copolymerized in addition to the perhaloolefin having 2 carbon atoms and vinyl acetate.
  7. 前記非フッ素系単量体が、オレフィン、ビニルエーテルおよびビニルエステルよりなる群から選ばれる少なくとも１種である請求項６記載の製造方法。 The production method according to claim 6, wherein the non-fluorine monomer is at least one selected from the group consisting of olefin, vinyl ether and vinyl ester.
  8. 前記非フッ素系単量体が、架橋性基含有単量体と架橋性基非含有単量体である請求項７記載の製造方法。 The production method according to claim 7, wherein the non-fluorine-based monomer is a crosslinkable group-containing monomer and a crosslinkable group-free monomer.
  9. 前記架橋性基含有単量体が、水酸基含有ビニル単量体または不飽和カルボン酸である請求項８記載の製造方法。 The method according to claim 8, wherein the crosslinkable group-containing monomer is a hydroxyl group-containing vinyl monomer or an unsaturated carboxylic acid.
PCT/JP2012/058238 2011-03-31 2012-03-28 Method for producing fluorine-containing copolymer WO2012133582A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP12764488.8A EP2692750A4 (en) 2011-03-31 2012-03-28 Method for producing fluorine-containing copolymer
US14/008,617 US20150240012A1 (en) 2011-03-31 2012-03-28 Method for producing fluorine-containing copolymer
CN2012800161337A CN103459441A (en) 2011-03-31 2012-03-28 Method for producing fluorine-containing copolymer
KR1020137028672A KR20130135990A (en) 2011-03-31 2012-03-28 Method for producing fluorine-containing copolymer

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-080672 2011-03-31
JP2011080672 2011-03-31

Publications (1)

Publication Number Publication Date
WO2012133582A1 true WO2012133582A1 (en) 2012-10-04

Family

ID=46931289

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/058238 WO2012133582A1 (en) 2011-03-31 2012-03-28 Method for producing fluorine-containing copolymer

Country Status (6)

Country Link
US (1) US20150240012A1 (en)
EP (1) EP2692750A4 (en)
JP (2) JP2012214761A (en)
KR (1) KR20130135990A (en)
CN (1) CN103459441A (en)
WO (1) WO2012133582A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016023269A (en) * 2014-07-23 2016-02-08 旭硝子株式会社 Production method of fluorine-containing resin aqueous dispersion
CN109851705A (en) * 2019-03-20 2019-06-07 济南大学 A kind of method that one kettle way prepares the controllable TFE copolymer of molecular weight

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02240155A (en) * 1989-03-15 1990-09-25 Dainippon Ink & Chem Inc Aqueous dispersion of fluoroolefin copolymer
JPH02240154A (en) * 1989-03-15 1990-09-25 Dainippon Ink & Chem Inc Aqueous dispersion of fluoroolefin copolymer
JPH0333148A (en) * 1989-06-30 1991-02-13 Dainippon Ink & Chem Inc Aqueous dispersion of fluorocopolymer
US5032656A (en) 1987-11-23 1991-07-16 Allied-Signal Inc. Fluorinated copolymer and barrier films
US5070162A (en) 1987-11-20 1991-12-03 Allied-Signal Inc. Copolymerization of vinyl acetate and a fluoromonomer in an aqueous medium
JPH0841413A (en) * 1994-08-01 1996-02-13 Central Glass Co Ltd Production of aqueous dispersion of fluororesin
WO2002010237A1 (en) 2000-07-27 2002-02-07 Asahi Glass Company, Limited Aqueous fluorocopolymer dispersion
US6512063B2 (en) 2000-10-04 2003-01-28 Dupont Dow Elastomers L.L.C. Process for producing fluoroelastomers
WO2005063827A1 (en) 2003-12-25 2005-07-14 Daikin Industries, Ltd. Process for producing fluoropolymer
US20070032591A1 (en) 2005-08-08 2007-02-08 Mehdi Durali Polymerization of fluoropolymers using alkyl phosphonate surfactants
JP3937449B2 (en) 1995-02-03 2007-06-27 イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー Fluoromonomer / functionalized hydrocarbon monomer copolymerization process and copolymer product

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE463666A (en) * 1942-10-26
US2468664A (en) * 1945-08-28 1949-04-26 Du Pont Tetrafluoroethylene copolymers
WO1989004847A1 (en) * 1987-11-20 1989-06-01 Allied-Signal Inc. Fluorinated copolymer and barrier films
FR2644466B1 (en) * 1989-03-15 1992-08-14 Solvay PROCESS FOR THE MANUFACTURE OF VINYLIDENE FLUORIDE POLYMERS AND USE OF VINYLIDENE FLUORIDE POLYMERS FOR THE FORMULATION OF PAINTS
US5955556A (en) * 1995-11-06 1999-09-21 Alliedsignal Inc. Method of manufacturing fluoropolymers
CN1229406C (en) * 2002-01-23 2005-11-30 大连明辰振邦氟涂料股份有限公司 Aqueous fluoric resin and its prepn and application
US20070100101A1 (en) * 2005-10-28 2007-05-03 Ming-Hong Hung Fluoroelastomers containing copolymerized units of vinyl esters
CN101434674B (en) * 2007-11-12 2013-05-29 上海博泰氟材料有限公司 Fluorine-containing water-dilutable resin prepared by nucleocapsid emulsion multicomponent copolymerization and coating thereof

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5070162A (en) 1987-11-20 1991-12-03 Allied-Signal Inc. Copolymerization of vinyl acetate and a fluoromonomer in an aqueous medium
US5032656A (en) 1987-11-23 1991-07-16 Allied-Signal Inc. Fluorinated copolymer and barrier films
JPH02240155A (en) * 1989-03-15 1990-09-25 Dainippon Ink & Chem Inc Aqueous dispersion of fluoroolefin copolymer
JPH02240154A (en) * 1989-03-15 1990-09-25 Dainippon Ink & Chem Inc Aqueous dispersion of fluoroolefin copolymer
JPH0333148A (en) * 1989-06-30 1991-02-13 Dainippon Ink & Chem Inc Aqueous dispersion of fluorocopolymer
JPH0841413A (en) * 1994-08-01 1996-02-13 Central Glass Co Ltd Production of aqueous dispersion of fluororesin
JP3937449B2 (en) 1995-02-03 2007-06-27 イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー Fluoromonomer / functionalized hydrocarbon monomer copolymerization process and copolymer product
WO2002010237A1 (en) 2000-07-27 2002-02-07 Asahi Glass Company, Limited Aqueous fluorocopolymer dispersion
US6512063B2 (en) 2000-10-04 2003-01-28 Dupont Dow Elastomers L.L.C. Process for producing fluoroelastomers
WO2005063827A1 (en) 2003-12-25 2005-07-14 Daikin Industries, Ltd. Process for producing fluoropolymer
US20070032591A1 (en) 2005-08-08 2007-02-08 Mehdi Durali Polymerization of fluoropolymers using alkyl phosphonate surfactants

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2692750A4 *

Also Published As

Publication number Publication date
JP2012214761A (en) 2012-11-08
EP2692750A1 (en) 2014-02-05
CN103459441A (en) 2013-12-18
US20150240012A1 (en) 2015-08-27
EP2692750A4 (en) 2014-10-29
KR20130135990A (en) 2013-12-11
JP2014132098A (en) 2014-07-17

Similar Documents

Publication Publication Date Title
JP5742384B2 (en) Method for producing fluoropolymer
EP1726599B1 (en) Process for producing fluoropolymer
JP5673541B2 (en) Method for producing fluoropolymer
EP1891153A2 (en) Aqueous process for making fluoropolymers
JP5598476B2 (en) Method for producing fluoropolymer
WO2008073686A1 (en) Aqueous process for making fluoropolymers
JP6225683B2 (en) Method for producing aqueous fluoropolymer dispersion
US9273172B2 (en) Method for producing a fluoroelastomer
WO2004065436A1 (en) Method for producing vulcanizable fluorine-containing elastomer
JP2014132098A (en) Method for producing fluorine-containing copolymer
JP5454470B2 (en) Method for producing fluoropolymer
JP5413479B2 (en) Hexafluoropropylene-vinyl acetate copolymer

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12764488

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 14008617

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 2012764488

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 20137028672

Country of ref document: KR

Kind code of ref document: A